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To cite this article: George F. Antonious & Matthew A. Patterson (2005) Napropamide Residues in Runoff and Infiltration
Water from Pepper Production, Journal of Environmental Science and Health, Part B: Pesticides, Food Contaminants, and
Agricultural Wastes, 40:3, 385-396, DOI: 10.1081/PFC-200047570
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Journal of Environmental Science and Health Part B, 40:385–396, 2005
Copyright C Taylor & Francis Inc.
ISSN: 0360-1234 (Print); 1532-4109 (Online)
DOI: 10.1081/PFC-200047570
Napropamide Residues in
Runoff and Infiltration Water
from Pepper Production
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Key Words: Soil; Sewage sludge; Biosolids; Yard waste; Pepper fruit quality; Mobility.
INTRODUCTION
Contamination of surface and groundwater by pesticides is of great concern. Ap-
plication of pesticides to agricultural fields may result in their transport into
surface waters via runoff or into groundwater through infiltration.[1,2] New soil
management practices are needed to develop and expand our knowledge and
385
386 Antonious and Patterson
may break down pesticides. Compost also has been shown to increase pesticide
sorption[6−8] and decrease pesticide leaching.[9,10]
The application of yard waste compost and sewage sludge (biosolids) to agri-
cultural soils helps minimize landfill disposal. The Environmental Protection
Agency (EPA) estimates that 31 million tons of yard wastes[11] and 15 million
metric tons of biosolids[12] are discarded annually in the United States. In ad-
dition to the large amount of space that is wasted, bacterial decomposition
of yard wastes produces methane gas and acidic leachates that increase the
mobility of other waste components. In the early 1990s, 11 states and the
District of Columbia instituted legislation banning the disposal of yard wastes
in landfills, and by 1999 this number had increased to 23 states.[13] This legisla-
tion, in combination with a growing number of composting facilities across the
United States, has led to a gradual decline in yard waste disposal since 1992.
Biosolid (sewage sludge) disposal also has decreased with increased recycling
efforts. Currently, 60% of all biosolids produced are recycled as soil amend-
ments for reclamation sites, forest lands, and agricultural lands. However, less
than 1% of all agricultural lands in the United States are amended with re-
cycled biosolids.[14] Recycling this material as soil amendments would reduce
the need for landfill disposal and/or incineration and reduce the impact of their
disposal methods on environmental quality.
The addition of yard waste compost to soils has been shown to increase
yields for a wide variety of crops including pepper,[15] kohlrabi,[16] sunflower,[17]
and tall fescue.[18] Increased crop yields are attributed to increased organic mat-
ter content and improvements in the physical properties of the soil after the
addition of composted materials. Improved physical properties of soil include
increased aggregate stability,[19] increased moisture holding capacity,[20] and re-
duced bulk density[21] to allow for more efficient use of the mineral fertilizer.
Biosolid amendments also have been shown to increase yields of tall fescue,[22]
and alfalfa.[23] On the other hand, decreases in yield, due to the impact of salt
and heavy metal toxicity of sewage sludge, have been shown in other crops in-
cluding corn[24] and bush beans.[25] The proportion of sewage sludge recycled
for agricultural use is growing steadily in the United States.[26] Nutrients in
sludge are used to replace commercial fertilizers, while sludge organic matter
has been reported to improve soil structure, reduce soil erosion, and improve
Napropamide Residues from Pepper Production 387
crop yield.[27] The objectives of this research were (1) to study the influence
of mixing native soil with yard waste compost and sewage sludge on the con-
centration of the herbicide napropamide in soil and its subsequent movement
into runoff and infiltration water, and (2) to study the impact of sewage sludge
(class-A biosolids) and yard waste compost on pepper yield and fruit quality.
A field study was conducted on a Lowell silty loam soil (2.8% organic matter,
pH 6.9) at Kentucky State University Research Farm, Franklin County,
Kentucky. The soil has an average of 12% clay, 75% silt, and 13% sand. Eigh-
teen (18) plots (universal soil loss equation [USLE] standard plots) of 22 ×
3.7 m each were established on a 10% slope. Plots were separated using metal
borders 20 cm above the ground level to prevent cross contamination between
treated and untreated plots. Three soil management practices, replicated six
times, were used: (1) yard waste compost made from yard and lawn trim-
mings, and vegetable remains (produced at Kentucky State University Re-
search Farm, Franklin County, KY) was mixed with native soil at 50 t acre−1
(on dry-weight basis) with a plowing depth of 15 cm, (2) sewage sludge (ob-
tained from Nicholasville Wastewater Treatment Plant, Nicholasville, KY) was
also mixed with native soil at 50 t acre−1 (on dry-weight basis), and (3) no-
mulch (NM) treatment (rototilled bare soil) was used for comparison purposes.
Devrinol 50-DF “napropamide” (Fig. 1) obtained from United Phosphorus, Inc.
(P.O. Box 570, Exton, PA; EPA Registration No. 10182-258-70506) was sprayed
as a preemergent herbicide at the rate of 4 lb of formulated product acre−1
using a 4-gallon portable backpack sprayer (Solo) equipped with one conical
nozzle operated at 40 p.s.i. and incorporated into the soil surface. Sweet pepper
(Capsicum annuum L. cv. Aristotle-X3R) seeds were obtained from Seedway
ples were used to determine soil moisture content to report the results on dry-
weight basis. For pesticide residue analysis, 30-g soil were shaken with 100 mL
of acetone for 1 h using a Multi-wrist shaker (Lab-Line Instruments, Inc.,
Melrose Park, IL, USA). The solvent was filtered through Whatman 934-AH
glass microfibre discs (Fisher Sci, Pittsburgh, PA) of 90 mm diameter, concen-
trated by rotary vacuum (Buchi Rotavapor Model 461, Switzerland) and N2 gas
stream evaporation for GC/NPD determination.
Runoff (soil-water suspension) was collected and quantified at the lower end
of each plot using a tipping-bucket runoff metering apparatus (Department of
Agricultural Engineering, University of Kentucky, Lexington, KY, USA). Ho-
mogeneous samples of runoff were collected in amber borosilicate glass bottles
and transported to the laboratory on ice in coolers. Sediment in runoff was de-
termined by weighing the sediments collected from a 1-L sample of runoff using
Whatman No.1 filter paper. Napropamide residues were extracted from sedi-
ment samples as described in soil analysis. Total runoff water lost per runoff
event, per each 0.02-acre plot, was used to measure napropamide concentration.
To monitor the presence of napropamide residues in the vadose zone (the
unsaturated water layer below the plant root), pan-lysimeters (Department of
Agricultural Engineering, University of Kentucky, Lexington, KY, USA) were
installed at the end of the experimental plots down the land slope at a depth
of 1.5 m. Infiltration water was collected in amber borosilicate glass bottles.
Duplicate of 500 mL aliquots were filtered through Whatman 934-AH glass mi-
crofibre discs using vacuum filtration. Napropamide residues were extracted
three times by liquid-liquid partition with 100, 60, and 40 mL of acetone-
methylene chloride mixture (1:1). CH2 Cl2 fractions (bottom layer) were com-
bined and passed over Na2 SO4 anhydrous, then evaporated to dryness using N2
stream and reconstituted in acetone for GC/NPD determination. Napropamide
residues were determined using a Hewlett-Packard model 5890A series II gas
chromatograph (Hewlett-Packard Co., Avondale, PA) equipped with an NP de-
tector. Samples were injected onto a BD-5 high resolution column (15 m × 0.53
mm i.d.) with 0.5 µm film thickness (J & W Scientific, Folson, CA). Operating
conditions were 230, 250, and 280◦ C for injector, oven, and detector, respectively.
Carrier gas (He) flow rate was 5.2 mL min−1 . Peak areas were determined on
a Hewlett-Packard model 3396 series II integrator. Quantification was based
Napropamide Residues from Pepper Production 389
on average peak areas of 1 µL injections obtained from external standard so-
lutions of napropamide ranging from 1 to 10 ng µL−1 . Under these conditions
retention time (Rt) of napropamide was 10.99 min. Peak identity was confirmed
by consistent retention time and coelution with standards under the conditions
described. Napropamide residues also were confirmed using GC/MSD which
showed spectral data with a molecular ion peak (M+ ) at m/z 271, along with
other characteristic fragment ion peaks (Fig. 2). Napropamide technical mate-
rial of 97.9% purity was obtained from Chem Service (660 Tower Lane, West
Chester, PA). Linearity over the range of concentrations was determined using
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regression analysis (R2 = 0.99). Standard solutions were used to spike blank
soil samples for evaluating the reproducibility and efficiency of the analyti-
cal procedures to recover napropamide residues. Recoveries (means ± SE) of
Figure 2: Electron impact mass spectrum of napropamide indicating the molecular ion of
m/z 271.
390 Antonious and Patterson
napropamide from fortified soil samples were 92.3 ± 4.3, 91.4 ± 5.0, and 82.5 ±
3.5% from soil mixed with yard compost, soil mixed with sewage sludge, and no-
mulch soil, respectively. Recoveries from water samples averaged 89.7 ± 3.2%.
Quality control (QC) samples included three field blanks to detect possible con-
tamination during sampling, processing, and analysis. The lack of napropamide
residues in the blank samples suggested there was no contamination from sam-
pling, processing, or laboratory procedures.
Peppers were harvested 72 days, 86 days, and 100 days after planting,
weighed, and the fruits were graded according to USDA standards for sweet
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peppers.[28] USDA standards require mature green sweet peppers that are firm,
well shaped, and free from defects. All peppers not meeting these requirements
were culled. The total number and weight of culled peppers from each treat-
ment were recorded. The remaining peppers were graded as US Fancy (at least
3 inches in diameter and 3.5 inches in length), US No. 1 (at least 2.5 inches in
diameter and 2.5 inches in length), and US No. 2 (<2.5 inches in diameter). Sta-
tistical comparisons were done between the three soil management practices
using the ANOVA procedure (SAS Institute, 2001).[29]
Figure 3: Napropamide residues in soil collected from the rhizosphere of pepper plants
during 30 days following spraying with Devrinol 50-DF. Statistical comparisons were done
between three soil management practices. Means accompanied by asterisks indicate a
significant difference (P < 0.05) between soil treatments at a given time using Duncan’s
LSD test (SAS Institute, 2001).[29]
Napropamide Residues from Pepper Production 391
Previous results have indicated that the sorption of pesticides was highest
in soils with the greatest content of organic matter.[8,30,31] Our results (data
not shown) have indicated that the organic matter contents were significantly
higher in soil mixed with sewage sludge (5.95%) and soil mixed with yard waste
compost (5.72%) compared to NM bare soil (2.7%). Addition of sludge also has
increased the soil pH roughly 1.5 units compared to native soil.[32] An increase
in soil pH can bring about strong adsorption on soil particles or, in some cases,
precipitation of Mn, Cu, and Zn among other metals, which in turn allows for
lower accumulation of these metals in plant tissues.[33] Application of compost
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Figure 4: Volume of runoff water and napropamide residues in runoff water (upper graph)
and runoff sediment and napropamide residues in sediment (lower graph) from pepper
grown on erodible land under three soil management practices. Statistical comparisons
were done between three soil management practices. Bars accompanied by different
letter are significantly different (P < 0.05) from each other using Duncan’s LSD test (SAS
Institute, 2001).[29]
392 Antonious and Patterson
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retarded by the two compost treatments (sewage sludge and yard waste com-
post) along the land slope that would otherwise have been transported downhill
into streams and rivers. However, yard waste compost also increased water in-
filtration and napropamide residues in the vadose zone (Fig. 5), as indicated by
the volume of water collected in the pan-lysimeters installed at the lower end
of each plot.
Yard waste compost is rich in nutrients and organic matter.[32] Treatments
high in organic matter produced high pepper yield (Fig. 6). Organic substances
Figure 6: Yield of pepper grown under three soil management practices. Statistical
comparisons were done between the three soil management practices for each pepper
class or total yield. Bars accompanied by different letter in each class or total marketable
yield are significantly different (P < 0.05) from each other using Duncan’s LSD test (SAS
Institute, 2001).[29]
Napropamide Residues from Pepper Production 393
and nutrients in compost support a vast population of soil organisms that
“mine” for soil minerals. Evidence of enhanced microbial activity in the rhi-
zosphere of plants grown with yard waste compost has been reported.[36,37] The
effects of compost application on crop yield are derived from availability of
nutrients in compost (particularly N). Availability of soluble P also increased
following addition of compost.[38] Total pepper yield from yard waste compost
amended soils was significantly higher than yields from either the unamended
or sludge amended soils. Total yield from sludge and no-mulch treatments were
not significantly different. The use of sewage sludge in land farming must in-
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Figure 7: Number of pepper fruits obtained under three soil management practices.
Statistical comparisons were done between three soil management practices for each
pepper class or total marketable number. Bars accompanied by different letter in each
class or total yield are significantly different (P < 0.05) from each other using Duncan’s LSD
test (SAS Institute, 2001).[29]
394 Antonious and Patterson
chemical movement through soil. A strong positive relationship was found be-
tween napropamide concentration and DOM content in soil leachates.[39,40]
DOM, therefore, can affect the distribution of solutes between soil solution
and sorbed phases and the availability and environmental fate of the so-
lutes. The increased napropamide movement through the soil mixed with
yard waste compost into the vadose zone (Fig. 5) could be attributed to
the formation of napropamide-DOM complexes that lack adsorption affin-
ity for the solid phase.[40,41] A larger fraction of napropamide mass moved
horizontally on the soil surface in the NM bare soil through runoff water
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as compared to yard waste or sewage sludge mixed soils (Fig. 4), and this
counteracts the concentration of napropamide detected in infiltration water
(Fig. 5). Napropamide seeping into the vadose zone was lowest in no-mulch
soil compared to compost treatments. This trend confirms that sorption of
napropamide increased with the soil clay content and not with organic matter
content.[3]
The mobility of any pesticide in soil is one of the principal parameters
controlling the extent to which a pesticide may represent a risk for surface and
groundwater contamination. The application of compost to agricultural soils is
practiced to minimize landfill disposal and the organic matter in compost helps
to improve soil fertility, but DOM derived from compost may complex with
pesticides such as napropamide and enhance their vertical transport through
the soil into groundwater. The perfect set of pesticide properties for preventing
pesticides from reaching groundwater would include a combination of low water
solubility and tight binding to soil particles.
ACKNOWLEDGMENTS
The authors would like to thank Samuel Mutisya, Robert Stone, Eddie Read,
and John Clay for their kind help in pepper harvest. This investigation was
supported by a grant from USDA/CSREES to Kentucky State University under
agreement No. KYX-10-03-37P.
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